201233822 六、發明說明： 【發明所屬之技術領域】 本發明關於一種含矽膜之成膜技術。更詳細而言，關 於一種含矽膜成膜用的濺鍍用靶材、使用其之高品質含矽 膜之成膜方法、以及具備該高品質含矽膜的空白光罩基材 【先前技術】 近年來，在半導體加工技術領域之中，電路圖案隨著 大規模積體電路的高積體化等而微細化，因此在構成電路 的配線圖案的細線化、或構成單元的層間配線所用的接觸 孔圖案的微細化技術方面的需求正日漸提高。 爲了因應這項需求，而將光蝕刻法所使用之曝光光線 波長化，由I射線短以至於KrF準分子雷射，進一步而言 ，目前最先進的工業加工是採用 ArF準分子雷射（193 nm )° 在通常使用的光蝕刻法中，藉著使由光源所產生的光 線透過光罩，而製作出光線圖案，將其照射在光阻膜，而 在用來對被加工基板加工所形成的光阻膜上進行圖案曝光 。此時所使用的光罩，是爲了形成如上述般微細的圖案而 使用，進一步而言，是作_爲加工圖案的原圖，因此必須具 有極高的精密度。因此，對於構成光罩製造所使用的空白 材料（空白光罩基材）的膜而言，需要可得到高加工精密 度的膜，以及需要缺陷極少的膜。 -5- 201233822 關於空白光罩基材的構成要素其中之一的遮光膜的材 料’容易得到闻加工精密度的膜的矽系材料開始受到矚目 。過去以來是使用矽系材料作爲製作半色調相偏移光罩時 的半色調相偏移膜的成膜用材料（專利文獻1 :曰本特開 平7- 1 4063 5號公報）。以含有經過氮化或氧化的鉬的矽 系材料進行成膜，所得到的光學膜具有的優點爲透光特性 的控制性闻、以及容易得到高加工精密度。 這樣的砂系材料可藉著氟系乾式蝕刻進行加工，與以 往遮光膜的成膜一直以來所使用的鉻系材料相比之下，對 於20〇nm以下的曝光光線的遮光特性較優異，且不易對光 阻圖案造成傷害（專利文獻2:日本特開2〇〇7_241〇65號 公報）。 另外’矽系材料膜在爲了進行更高精密度的加工而與 使用蝕刻光罩的技術組合的情況中亦爲有利的。亦即發現 了在以鉻系材料膜作爲蝕刻光罩而對矽系材料的遮光膜實 施加工的情況中，與以矽系材料膜作爲蝕刻光罩，對鉻系 材料的遮光膜實施加工的情況相比之下，圖案依賴性或側 触刻所造成的加工誤差較小（專利文獻3 :日本特開 2007-24 1 060號公報）。因此，矽系材料之遮光膜可期待 成爲下一代的遮光膜，用來代替以往的鉻系材料的遮光膜 〇 矽系材料膜的成膜，一般而言可採用矽系材料之灘鍍 用祀。這種矽系材料之濺鍍用靶有例如矽單體的靶（專利 文獻4:日本特開2004-301993號公報）、或者含有過渡 201233822 金屬的矽系材料膜之成膜所使用的含有過渡金屬的矽系靶 等’然而已知若使用矽單體的濺鍍用靶進行成膜，則由於 靶材的導電率低，會在濺鍍步驟中產生顆粒，所得到的光 學膜容易產生顆粒缺陷。 爲了抑制由這種矽單體的濺鍍用靶產生顆粒，有幾項 提案已經進行，例如在日本特開2002-72443號公報（專 利文獻5 )中，提出了一種單結晶矽之濺銨用靶之使用， 在日本特開2003-322955號公報（專利文獻6)中，提出 了 一種在矽單體中添加施體雜質或受體雜質而降低比電阻 的濺鍍用靶之使用。 [先前技術文獻] [專利文獻] [專利文獻1 ]日本特開平7 - 1 4 0 6 3 5號公報 [專利文獻2]日本特開2007-241065號公報 [專利文獻3]日本特開2007-241060號公報 [專利文獻4]日本特開2004-301993號公報 [專利文獻5]日本特開2002-72443號公報 [專利文獻6]日本特開2〇〇3_322955號公報 【發明內容】 [發明所欲解決之課題] 附帶一提’在如光罩的圖案尺寸爲45nm以下這種極 微細的圖案這樣的情況下，爲了製造這種光罩所使用的空 白光罩基材’需要比目前還高的低缺陷性（高品質性）。 201233822 因此’在空白光罩基材之製造步驟之中， 易產生顆粒的矽系材料之靶使矽系材料膜 要比目前還高的抑制顆粒導致的缺陷的技 本發明鑑於這樣的課題而完成，其目 種矽靶材，其在濺鍍步驟中不易產生顆粒 ’以謀求成膜的含矽膜之低缺陷化（高品 [用於解決課題之手段] 爲了解決上述課題，本發明所關連之 使用於含矽膜之成膜的矽靶材，而前述矽 電阻爲20Ω .cm以上。 前述矽靶材的導電型宜爲η型。另外 爲單結晶。例如前述矽靶材爲藉由FZ法 晶砂。 另外，本發明所關連之含矽膜之成膜 :使用在室溫的比電阻爲20 Ω · cm以上的 濺鍍法使含矽膜成膜。 前述矽靶材之導電型宜爲η型。另外 爲單結晶。前述含矽膜之成膜可在含有反 中實行，反應性氣體係含有氧及氮之中至 鍍法宜爲DC濺鍍法。 本發明所關連之空白光罩基材係具備 膜的含矽膜。 在使用濺鍍中容 成膜的情況，需 術。 標之在於提供一 ，使用此矽靶材 質化）。 濺鍍用靶材，係 靶材在室溫的比 ，前述矽靶材宜 養晶而成的單結 方法，其特徵爲 矽靶材，並藉由 ，前述矽靶材宜 應性氣體的環境 少一種。前述濺 藉由上述方法成 201233822 [發明之效果] 在本發明中，由於設計成使用在室溫的比電阻爲20 Ω •cm以上的矽靶材，而使含矽膜濺鍍成膜，因此經過成膜 步驟，放電特性得以改善，其結果，含矽膜中的顆粒缺陷 數減少。 藉此可提供一種低缺陷且高品質的含矽膜，亦可利用 作爲空白光罩基材的遮光膜或相偏移膜等。 【實施方式】 使用矽靶材進行濺鍍時所產生的顆粒，其發生的原因 一般而言認爲是在靶上的電弧放電。關於這點，在日本特 開2003 -3 2295 5號公報（專利文獻6)中也記載了若靶的 導電性低，則在靶表面不易施加電壓，放電變得不安定， 在靶上容易發生電弧放電，因此變得容易產生顆粒，在專 利文獻6所揭示的發明中，爲了減少這種顆粒的產生，而 設計成使用比電阻爲〇. 1 Ω · cm以下的矽靶。 本發明人等爲了進一步的減輕濺鍍步驟中所產生的顆 粒導致光學膜中的缺陷，反覆檢討之中，發現與使用比電 阻爲0· 1 Ω · cm以下這種低電阻値（高導電性）矽靶的專 利文獻6所揭示的發明相反地，藉著使用高電阻値（低導 電性）矽靶，反而能夠得到顆粒導致的缺陷少的含矽膜， 以至於完成本發明。 在本發明中，含矽膜之成膜所使用的矽靶材，是採用 較高電阻値（低導電性）、在室溫的比電阻爲2 0 Ω · Cm以 -9- 201233822 上的濺鍍用靶材。亦即，以往的構想如專利文獻6所揭示 般，藉著抑制由於靶材表面的高電阻化所引起的電弧放電 的發生來減少顆粒的產生，在本發明中選擇了與其相反的 比電阻値，而藉由使用在室溫的比電阻爲20 Ω · cm以上的 濺鍍用靶材進行成膜，如後述般，可得到顆粒缺陷少的含 矽膜。 從放電安定性的觀點看來，這種矽靶材以添加了微量 的磷或砷等的施體元素的η型導電型物質爲佳。在這種矽 靶材採用單結晶矽的情況，由於不含粒界，因此抑制顆粒 產生的效果高。尤其以F Ζ法養晶而成的單結晶矽，其氧 含量極低，適合作爲本發明之矽靶材。 在以下內容中，以本發明之含矽膜作爲構成空白光罩 基材的光學膜而作說明，然而本發明並不受其所限定。 含矽膜可利用作爲例如空白光罩基材之相偏移膜或遮 光膜。此處，遮光膜是指在作爲光罩使用時’用以使穿透 設置有該遮光膜的區域的光線變成實際上對於曝光沒有幫 助的光學膜’因此’成膜在透明基板上的光線吸收膜對於 曝光光線的光學濃度（〇Ptica丨Density)的總計爲2·0以 上，較典型而言爲2.5以上。 這種含矽膜有例如：矽單體膜、或在砂之外加上含有 氧或氮作爲主要的構成元素之膜。這種含砂膜’通常藉由 使含矽原子的靶材在含有反應性氣體的環境中進行反應性 濺鍍而成膜’該反應性氣體因應必要添加了氧或氮。此外 ，濺鍍的手段係以D c濺鍍法爲佳’其被認爲容易得到產 -10- 201233822 生的顆粒少且品質高的膜。 在含矽膜之成膜所使用的靶材中，對應於含矽膜的組 成’有矽單體的靶材（矽靶材）或含有過渡金屬的矽系材 料的耙材等。 除了欲使不含過渡金屬的含矽膜成膜的情況之外，欲 使·過渡金屬相對於矽的含有比往膜的深度方向作變化的情 況’或欲使過渡金屬相對於矽的含有比降至非常低的情況 等’可使用實際上不含過渡金屬的矽靶材。 附帶一提，在目前最先進的半導體加工用蝕刻法中， 是使用ArF準分子雷射作爲曝光光線。在此曝光波長區域 ’爲了確保作爲相偏移膜所須要的透過率，在使這種膜成 膜時，需要所含過渡金屬比率比過去以來所使用的含有過 渡金屬的矽材料更低的材料。另外，遮光膜的材料過去以 來是採用鉻系材料，·然而逐漸發現了從遮光性能或加工性 能的觀點看來以矽系材料較爲優異，可知含矽的比率愈提 高，則化學耐性變得愈高。 在這樣的背景之下，在使含矽膜濺鏟成膜時，使用矽 單體的靶材（矽靶材）的必要性正逐漸提高。 但是，使用矽單體的靶材（矽靶材），在藉由DC濺 鏟法進行反應性濺鍍成膜的情況下，若該靶材的導電性低 ，則放電變得不安定，異常放電變得容易發生。而且還發 現在這樣的放電狀態下成膜而得的含矽膜，會含有許多顆 粒所導致的缺陷（顆粒缺陷）。考慮到這些理由，在專利 文獻6所揭示的發明中，藉由添加施體或受體這些雜質， -11 - 201233822 使用提高導電性（低電阻率）的矽靶材，成膜安定性及減 少顆粒的產生，而提升生產性。 本發明人等，爲了藉由使用矽靶材的D C濺鍍成膜得 到顆粒缺陷少的含矽膜而進行檢討，在過程中確認了下述 事實。首先，如以往的報告例所述，如果定爲使用比電阻 在1 Ω . cm以下的矽靶材，則容易得到安定的放電，異常 放電也不易發生，比電阻爲1 5 Ω . cm左右的矽靶材則極難 得到安定的放電。但是，若將比電阻進一步提高到高於1 5 Ω · cm，則放電特性得以改善，在比電阻爲20 Ω · cm以上 的區域，所得到的含矽膜中之顆粒缺陷數減少。若將矽靶 材之比電阻定爲5 0 Ω · cm以上，則此顆粒缺陷數的減少變 得顯著。 使用比電阻高的矽靶材所產生的減少顆粒缺陷數的效 果，其理由未必明顯可知，而本發明人等作出下述般的推 測。 在濺鍍成膜步驟中，具有高能量的粒子等（電漿）會 照射在靶上，而若這些高能量粒子衝撞到如矽般的半導體 結晶，則產生載體（電子或電洞）。所以，在使用矽靶進 行濺鍍成膜時，會在靶內產生載體。 所產生的載體會藉由所施加的電壓而在靶內移動（擴 散），而若擴散中的載體衝撞到矽的結晶格子，則更進一 步產生載體。於是由於這種產生載體的現象重覆進行’載 體數目會逐漸增大。 靶材所含的雜質濃度愈低，則一旦產生的載體在矽結 -12- 201233822 晶中擴散的距離變得愈長，因此矽靶材的比電阻愈高，則 載體的增加變得愈爲顯著。其結果，比電阻高的矽靶材在 電漿中相對而言導電性變高，異常放電變得不易發生。 另一方面，比電阻低的矽靶材，在矽結晶中相對而言 含有許多作爲受體的硼（B)或作爲施體的磷（P)等的雜 質，故導電性會藉由因這些雜質所產生的載體而提高，藉 此放電安定性得以改善。 但是，這種比電阻低的矽靶材表面容易與環境中的反 應性氣體發生反應，因此在靶表面容易以較厚的膜厚形成 氧化膜等的高電阻膜。 相對於此，如本發明申請所關連之矽靶材般，比電阻 較高的靶材的靶表面不易與環境中的反應性氣體發生反應 ，即使在靶表面形成氧化膜等的高電阻率的膜，也只是厚 度較薄的膜。因此，在至濺鍍成膜結束的期間，容易維持 安定的放電狀態。但是，上述機制在目前的時間點只是本 發明人等的推測，在解釋本發明方面並不會產生任何限制 〇 本發明所關連之矽靶材爲多結晶或非晶質的物質皆可 ’然而如果設定爲單結晶的物質，則由於沒有結晶粒界， 因此會有可實現較安定的放電狀態這樣的優點。另外，藉 由FZ法養晶而成的單結晶矽由於氧含量低，因此爲適合 作爲高純度矽靶材的材料。 本發明所關連之矽靶材，由於比電阻較高，因此在矽 中所含摻雜物的濃度低。所以，只要滿足比電阻爲20 Ω . -13- 201233822 cm以上這樣的條件，就不會因爲摻雜物的種類（導電型 )或濃度（導電率）而損及本發明的效果，而從得到安定 的放電特性的觀點看來，係以含有施體雜質的η型物質佳 含矽膜之濺鍍成膜，除了單獨使用或使用多種本發明 之矽靶材來進行之外，還可同時使用矽靶材與含有過渡金 屬與矽的靶材，或同時使用矽靶材與過渡金屬靶材來進行 〇 在同時使用矽靶材與含有過渡金屬與矽的靶材的情況 ，後者靶材之組成，可因應目標之膜組成而適當地選擇。 此情況下，過渡金屬沒有必要侷限爲一種。在含有多種過 渡金屬的情況，各種過渡金屬與矽的含有比率，每種過渡 金屬可爲不同。這樣的靶材，一般而言藉由燒結法來製造 〇 遮光膜或相偏移膜之成膜用靶材所含有的過渡金屬可 例示例如鈦、釩、鈷、鎳、鉻、鈮、鉬、給、鉅及鎢等。 從所得到的膜之乾式蝕刻加工性的觀點看來，以鉬爲佳。 本發明所關連之含矽膜，係使用上述在室溫的比電阻 爲20Ω·(：ιη以上的矽靶材，並藉由濺鑛法成膜。這種含矽 膜可例示氧化矽、氮化矽、氮氧化矽、過渡金屬矽氧化物 、過渡金屬矽氮化物、過渡金屬矽氮氧化物等。這種膜亦 可含有碳、氦或氫等的輕元素。 含矽膜中所含的過渡金屬相對於矽的比率，可藉由其 成膜所使用的靶材與施加至靶材的電力來作調整。另外， -14 - 201233822 含砂膜中之氧、氮或碳等的輕元素含量，可藉由後述灘鑛 氣體的調整而作控制。 本發明所關連之含矽膜之組成可依照目標之膜機能而 適當地調整，而遮光膜中’具有高遮光機能的膜之組成’ 宜爲矽占10原子％以上95原子％以下，尤其是30原子°/〇 以上9 5原子％以下，氧占〇原子％以上5 0原子％以下’尤 其是〇原子％以上30原子％以下，氮占〇原子％以上40原 子％以下，尤其是〇原子％以上20原子％以下’碳占0原 子％以上2 0原子％以下’尤其是〇原子％以上5原子％以 下，過渡金屬占〇原子％以上3 5原子％以下’尤其是1原 子％以上20原子％以下。 遮光膜中’具有抗反射機能的膜之組成’宜爲矽占10 原子％以上80原子％以下’尤其是30原子％以上50原子 %以下，氧占〇原子％以上6 0原子％以下’尤其是0原子 %以上40原子％以下，氛占〇原子％以上57原子％以下’ 尤其是20原子％以上50原子％以下’碳占〇原子％以上 2 0原子％以下，尤其是0原子％以上5原子％以下’過渡 金屬占〇原子％以上35原子％以下’尤其是1原子％以上 20原子％以下。 可發揮吸收光線的相偏移膜的機能的膜之組成’宜爲 石夕占10原子％以上95原子以下’尤其是20原子％以上 95原子％以下，氧占〇原子％以上6〇原子％以下’尤其是 〇原子％以上4 0原子％以下’氮占〇原子％以上5 〇原子％ 以下，尤其是0原子％以上4 0原子％以下’碳占0原子％ -15- 201233822 以上2 0原子％以下，尤其是〇原子％以上5原子％以下， 過渡金屬占〇原子％以上3 5原子％以下’尤其是1原子％ 以上2 0原子％以下。201233822 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a film forming technique containing a ruthenium film. More specifically, the present invention relates to a sputtering target for a ruthenium film-forming film, a high-quality ruthenium-containing film formation method using the same, and a blank reticle substrate having the high-quality ruthenium-containing film. In recent years, in the field of semiconductor processing technology, the circuit pattern is refined with the integration of a large-scale integrated circuit, etc., and therefore, the wiring pattern of the circuit is thinned or the interlayer wiring of the constituent unit is used. The demand for micronization technology of contact hole patterns is increasing. In order to meet this demand, the exposure light used in photolithography is wavelength-limited, from I-rays to KrF excimer lasers. Further, the most advanced industrial processing is the use of ArF excimer lasers (193). Nm ) ° In the commonly used photolithography method, a light pattern is produced by passing light generated by a light source through a mask, and is irradiated on the photoresist film to be processed for processing the substrate to be processed. Pattern exposure is performed on the photoresist film. The mask used in this case is used to form a fine pattern as described above, and further, it is an original image of the processed pattern, and therefore it is required to have extremely high precision. Therefore, for a film constituting a blank material (blank mask substrate) used for the manufacture of a mask, a film having high processing precision and a film requiring few defects are required. -5-201233822 The material of the light-shielding film which is one of the constituent elements of the blank mask base material has been attracting attention. In the past, a bismuth-based material has been used as a film-forming material for a halftone phase shift film in the case of producing a halftone phase shift mask (Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. The film is formed of a lanthanum material containing nitriding or oxidized molybdenum, and the obtained optical film has an advantage of controlling the light-transmitting property and easily obtaining high processing precision. Such a sand-based material can be processed by fluorine-based dry etching, and is excellent in light-shielding characteristics for exposure light of 20 nm or less, compared with a chromium-based material which has been conventionally used for film formation of a light-shielding film. It is not easy to cause damage to the resist pattern (Patent Document 2: JP-A-H07-241-65). Further, the ruthenium-based material film is also advantageous in combination with a technique using an etch mask for processing with higher precision. In the case where the light-shielding film of the lanthanoid material is processed by using the chromium-based material film as an etching mask, the case where the light-shielding film of the chromium-based material is processed by using the lanthanoid material film as an etching mask In contrast, the processing error caused by the pattern dependency or the side touch is small (Patent Document 3: JP-A-2007-24 1 060). Therefore, the light-shielding film of the lanthanoid material is expected to be the next-generation light-shielding film, and it is used for the film formation of the light-shielding film lanthanum material film of the conventional chrome-based material. . The target for sputtering of the lanthanoid material includes a target of, for example, a ruthenium monomer (Patent Document 4: JP-A-2004-301993) or a film containing a transitional 201233822 metal film. Metal lanthanum target or the like 'However, if a sputtering target is used for film formation, since the conductivity of the target is low, particles are generated in the sputtering step, and the obtained optical film is likely to generate particles. defect. In order to suppress the generation of particles by the target for sputtering of such a ruthenium monomer, several proposals have been made. For example, in Japanese Laid-Open Patent Publication No. 2002-72443 (Patent Document 5), a single crystal ruthenium is proposed. In the use of a target for sputtering in which a specific impurity or a receptor impurity is added to a ruthenium monomer to reduce the specific resistance, a target of a sputtering target is proposed in JP-A-2003-322955 (Patent Document 6). [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2007-241065 [Patent Document 2] JP-A-2007-241065 [Patent Document 3] JP-A-2007- [Patent Document 4] Japanese Laid-Open Patent Publication No. 2004-72443 [Patent Document 5] JP-A-2002-72443 [Patent Document 6] [Invention] [Invention] Problem to be Solved] In the case where the pattern size of the photomask is 45 nm or less, the blank mask substrate used for manufacturing such a mask needs to be higher than the current one. Low defect (high quality). 201233822 Therefore, in the manufacturing process of the blank mask substrate, the target of the lanthanoid material which is easy to generate particles, the lanthanide material film is higher than the current one to suppress the defects caused by the particles, and the present invention is completed in view of such a problem. In view of the above problems, the present invention relates to the target of the ruthenium target, which is less likely to generate particles in the sputtering step to reduce the defects of the ruthenium-containing film which is formed into a film (high-quality means for solving the problem) It is used for a tantalum target containing a tantalum film, and the tantalum resistance is 20 Ω·cm or more. The conductive type of the ruthenium target is preferably η type, and is also a single crystal. For example, the ruthenium target is FZ. Further, in the film formation of the ruthenium-containing film according to the present invention, the ruthenium-containing film is formed by a sputtering method having a specific resistance at room temperature of 20 Ω · cm or more. It is a η type, and is a single crystal. The film formation of the ruthenium-containing film can be carried out in the middle of the reaction, and the reactive gas system contains oxygen and nitrogen. The plating method is preferably a DC sputtering method. The cover substrate is a film containing a film. In the case of the plating film formation capacity, required surgery. The standard is to provide a use of this silicon target qualitative). The target for sputtering is a single-junction method in which the target of the target is at room temperature, and the target is preferably crystallized, and is characterized by a target of a suitable gas of the target target. One less. The above-mentioned method is formed by the above method into 201233822. [Effects of the Invention] In the present invention, since the tantalum-containing film is sputter-deposited by using a tantalum target having a specific resistance of 20 Ω·cm or more at room temperature, After the film formation step, the discharge characteristics are improved, and as a result, the number of particle defects in the ruthenium-containing film is reduced. Thereby, a low defect and high quality ruthenium containing film can be provided, and a light shielding film or a phase shift film which is a blank reticle substrate can be used. [Embodiment] The cause of the occurrence of particles generated by sputtering using a ruthenium target is generally considered to be an arc discharge on a target. In the Japanese Patent Publication No. 2003-32 2295 5 (Patent Document 6), it is also described that when the conductivity of the target is low, voltage is less likely to be applied to the target surface, the discharge becomes unstable, and the target is likely to be generated. In the invention disclosed in Patent Document 6, in order to reduce the generation of such particles, a ruthenium target having a specific resistance of 〇1 Ω·cm or less is designed. In order to further reduce the defects in the optical film caused by the particles generated in the sputtering step, the present inventors have found that low resistance 値 (high conductivity) with a specific resistance of 0·1 Ω·cm or less is found. In contrast to the invention disclosed in Patent Document 6 of the target, the use of a high-resistance 低 (low-conductivity) ruthenium target, on the contrary, can obtain a ruthenium-containing film having few defects due to particles, so that the present invention has been completed. In the present invention, the ruthenium target used for the film formation of the ruthenium film is a high resistance 値 (low conductivity), and the specific resistance at room temperature is 20 Ω · Cm to -9 - 201233822 Target for plating. In other words, as disclosed in Patent Document 6, the generation of particles is reduced by suppressing the occurrence of arc discharge due to the increase in the resistance of the surface of the target. In the present invention, the opposite specific resistance is selected. On the other hand, by using a target for sputtering having a specific resistance at room temperature of 20 Ω·cm or more, a ruthenium-containing film having few particle defects can be obtained as will be described later. From the viewpoint of discharge stability, such a ruthenium target is preferably an n-type conductivity type substance to which a trace amount of a donor element such as phosphorus or arsenic is added. In the case where such a ruthenium target is a single crystal ruthenium, since the grain boundary is not contained, the effect of suppressing the generation of particles is high. In particular, a single crystal ruthenium which is crystallized by the F Ζ method has an extremely low oxygen content and is suitable as a ruthenium target of the present invention. In the following, the ruthenium-containing film of the present invention is described as an optical film constituting a blank reticle substrate, but the present invention is not limited thereto. The ruthenium-containing film can be utilized as, for example, a phase shift film or a light-shielding film of a blank reticle substrate. Here, the light-shielding film means that when used as a photomask, 'the light used to penetrate the region in which the light-shielding film is provided becomes an optical film which is practically not helpful for exposure', so the light absorption on the transparent substrate is formed. The total optical density (〇Ptica丨Density) of the film for the exposure light is 2.0 or more, and is typically 2.5 or more. Such a ruthenium-containing film is, for example, a ruthenium monomer film or a film containing oxygen or nitrogen as a main constituent element in addition to sand. Such a sand-containing film 'is usually formed by subjecting a target containing a ruthenium atom to a reactive sputtering in an environment containing a reactive gas. The reactive gas is optionally added with oxygen or nitrogen. Further, the sputtering method is preferably a D c sputtering method, which is considered to be easy to obtain a film having a small amount of particles and having a high quality. Among the targets used for the film formation of the ruthenium film, the composition corresponding to the ruthenium-containing film is a target having a ruthenium monomer (ruthenium target) or a ruthenium material containing a transition metal lanthanum material. In addition to the case where the transition metal-containing ruthenium-containing film is to be formed, the content of the transition metal relative to the ruthenium is changed from the depth direction of the film or the ratio of the transition metal to the ruthenium is desired. Down to very low conditions, etc. 'Use a target that does not actually contain transition metals. Incidentally, in the most advanced etching method for semiconductor processing, an ArF excimer laser is used as the exposure light. In the exposure wavelength region, in order to ensure the transmittance required as a phase-shifting film, when the film is formed into a film, a material having a transition metal ratio lower than that of a transition metal-containing germanium material used in the past is required. . In addition, the material of the light-shielding film has been made of a chrome-based material. However, it has been found that the lanthanoid-based material is excellent in terms of light-shielding performance and workability, and it is known that the higher the ratio of cerium-containing, the chemical resistance becomes The higher the height. Under such a background, the necessity of using a target of a ruthenium monomer (ruthenium target) is gradually increasing when a film containing a ruthenium film is formed into a film. However, when a target (tantalum target) using a ruthenium monomer is subjected to reactive sputtering by a DC sputtering method, if the conductivity of the target is low, the discharge becomes unstable and abnormal. The discharge becomes easy to occur. Further, it has been found that the ruthenium-containing film obtained by film formation in such a discharge state contains defects (particle defects) caused by many particles. In view of these reasons, in the invention disclosed in Patent Document 6, by adding an impurity such as a donor or a receptor, -11 - 201233822 uses a ruthenium target having improved conductivity (low resistivity) to form film stability and decrease. The production of particles improves productivity. The inventors of the present invention reviewed the fact that the ruthenium-containing film having few particle defects was obtained by sputtering using D C sputtering of a target, and the following facts were confirmed in the process. First, as described in the previous report example, if a ruthenium target having a specific resistance of 1 Ω·cm or less is used, it is easy to obtain stable discharge, and abnormal discharge is unlikely to occur, and the specific resistance is about 15 Ω·cm. It is extremely difficult to obtain a stable discharge from a target. However, if the specific resistance is further increased to more than 15 Ω · cm, the discharge characteristics are improved, and in the region where the specific resistance is 20 Ω · cm or more, the number of particle defects in the obtained ruthenium-containing film is reduced. If the specific resistance of the target is set to 50 Ω · cm or more, the reduction in the number of particle defects becomes remarkable. The reason for reducing the number of particle defects generated by the use of a ruthenium target having a higher specific resistance is not necessarily obvious, and the inventors of the present invention have made the following estimations. In the sputtering film forming step, particles (plasma) having high energy are irradiated onto the target, and if these high-energy particles collide with semiconductor crystals such as ruthenium, a carrier (electron or hole) is generated. Therefore, when a sputtering target is formed by using a ruthenium target, a carrier is generated in the target. The resulting carrier is moved (expanded) within the target by the applied voltage, and if the carrier in the diffusion collides with the crystalline lattice of the crucible, the carrier is further produced. Thus, the number of carriers will gradually increase due to the phenomenon in which the carrier is generated repeatedly. The lower the concentration of impurities contained in the target, the longer the distance at which the generated carrier diffuses in the yttrium-12-201233822 crystal, so the higher the specific resistance of the ruthenium target, the more the carrier increases. Significant. As a result, the bismuth target having a higher specific resistance has a higher conductivity in the plasma, and the abnormal discharge is less likely to occur. On the other hand, a ruthenium target having a lower specific resistance contains relatively many impurities such as boron (B) as a acceptor or phosphorus (P) as a donor in the ruthenium crystal, so conductivity is caused by these. The carrier generated by the impurities is increased, whereby the discharge stability is improved. However, since the surface of the ruthenium target having a low specific resistance easily reacts with the reactive gas in the environment, it is easy to form a high-resistance film such as an oxide film on the surface of the target with a thick film thickness. On the other hand, as with the target of the target associated with the present invention, the target surface of the target having a higher specific resistance is less likely to react with the reactive gas in the environment, and a high resistivity such as an oxide film is formed on the surface of the target. The film is also a thin film. Therefore, it is easy to maintain a stable discharge state during the period from the end of the sputtering film formation. However, the above mechanism is only speculation by the present inventors at the present time point, and does not impose any limitation in explaining the present invention. However, the target material to which the present invention relates is polycrystalline or amorphous. If it is set as a single crystal substance, since there is no crystal grain boundary, there is an advantage that a relatively stable discharge state can be achieved. Further, the single crystal ruthenium which is crystallized by the FZ method is suitable as a material for a high-purity ruthenium target because of its low oxygen content. The tantalum target associated with the present invention has a low specific resistance and therefore has a low concentration of dopants contained in the crucible. Therefore, as long as the specific resistance is 20 Ω -13 - 201233822 cm or more, the effect of the present invention is not impaired by the type (conductivity) or concentration (conductivity) of the dopant. From the viewpoint of stable discharge characteristics, it is possible to use a sputter film of a n-type substance containing a donor impurity as a ruthenium-containing film, and to use it simultaneously or separately using a plurality of ruthenium targets of the present invention.矽 target and target containing transition metal and ruthenium, or simultaneous use of ruthenium target and transition metal target for the simultaneous use of ruthenium target and target containing transition metal and ruthenium, the composition of the latter target It can be appropriately selected in accordance with the film composition of the target. In this case, the transition metal is not necessarily limited to one. In the case of a variety of transition metals, the ratio of the various transition metals to rhenium may vary from one transition metal to another. Such a target is generally a transition metal contained in a target for film formation of a ruthenium-shielding film or a phase-shift film by a sintering method, and examples thereof include titanium, vanadium, cobalt, nickel, chromium, ruthenium, molybdenum, and the like. Giving, giant and tungsten. From the viewpoint of dry etching processability of the obtained film, molybdenum is preferred. The ruthenium-containing film to which the present invention relates is formed by using a ruthenium target having a specific resistance at room temperature of 20 Ω·(: ηη or more, and is formed by a sputtering method. The ruthenium-containing film can be exemplified by ruthenium oxide and nitrogen. Plutonium, bismuth oxynitride, transition metal lanthanum oxide, transition metal lanthanum nitride, transition metal lanthanum oxynitride, etc. The film may also contain light elements such as carbon, ruthenium or hydrogen. The ratio of the transition metal to the ruthenium can be adjusted by the target used for film formation and the electric power applied to the target. In addition, -14 - 201233822 contains light elements such as oxygen, nitrogen or carbon in the film. The content can be controlled by the adjustment of the beach mineral gas described later. The composition of the ruthenium-containing film associated with the present invention can be appropriately adjusted according to the target film function, and the composition of the film having a high light-shielding function in the light-shielding film Preferably, the yttrium accounts for 10 atom% or more and 95 atom% or less, particularly 30 atom%/〇 or more and 9.5 atom% or less, and oxygen accounts for 〇 atom% or more and 50 atom% or less 'especially 〇 atom% or more and 30 atom% or less. Nitrogen accounts for more than 40% by atom of yttrium atom, especially It is 〇 atom% or more and 20 atom% or less 'carbon accounts for 0 atom% or more and 2 atom% or less', especially 〇 atom% or more and 5 atom% or less, and transition metal accounts for 〇 atom% or more and 3-5 atom% or less 'especially 1 atom. % or more and 20 atom% or less. The composition of the film having an anti-reflection function in the light-shielding film is preferably 10 atom% or more and 80 atom% or less, especially 30 atom% or more and 50 atom% or less, and oxygen accounts for more than 〇 atom%. 60 atom% or less 'especially 0 atom% or more and 40 atom% or less, and the atmosphere accounts for 〇 atom% or more and 57 atom% or less ' Especially 20 atom% or more and 50 atom% or less 'carbon 〇 atom%% or more 2 0 atom% or less In particular, 0 atom% or more and 5 atom% or less 'transition metal accounts for 〇 atom% or more and 35 atom% or less', especially 1 atom% or more and 20 atom% or less. The composition of the film which functions as a phase shift film which absorbs light 'Yesi Shi Xizhan accounts for 10 atom% or more and 95 atoms or less', especially 20 atom% or more and 95 atom% or less, and oxygen accounts for 〇 atom% or more and 6 〇 atom% or less 'especially 〇 atom% or more 4 0 atom The following 'nitrogen accounts for 〇 atom% or more and 5 〇 atom% or less, especially 0 atom% or more and 4 atom% or less 'carbon occupies 0 atom% -15-201233822 or more 2 0 atom% or less, especially 〇 atom% or more and 5 atoms % or less, the transition metal accounts for 5% by atom or more and 35% by atom or less, especially 1 atom% or more and 2 atom% or less.
關於本發明的濺鍍方法，並不受特別限制，而以DC 濺鍍爲佳。此外，DC濺鍍爲DC濺鍍或脈衝DC濺鍍皆可 〇 本發明所關連之含矽膜，係使用在室溫的比電阻係2 0 Ω · cm以上的矽靶材，在例如含有反應性氣體的環境中進 行反應性濺鍍成膜，該反應性氣體係含有氧及氮之中至少 一者。含有氧的氣體可例示氧氣、氧化氮氣體（氮的氧化 數並未受到特別限制）、一氧化碳氣體、二氧化碳氣體等 。另外，含氮的氣體可例示氮氣、氧化氮氣體（氮的氧化 數並未受到特別限制）、氨氣等。此外，與這些氣體亦可 同時使用氬、氙或氨這些惰性氣體。 這樣的濺鍍氣體，爲了得到目標之膜組成、或放電安 定性可經過適當調整。氣壓的範圍只要定在例如0.0 1 P a -1 0 P a即可。 本發明所關連之空白光罩基材，係具備上述本發明之 含矽膜作爲遮光膜或相偏移膜等的光學膜。本發明之含矽 膜亦可用來作爲以高精密度將遮光膜蝕刻加工所用的硬式 光罩膜’或者作爲像是設置於透明基板與遮光膜之間的蝕 刻阻擋膜這樣的補助膜。 本發明所關連之矽靶材與以往的矽靶材相反地，其電 阻値選擇在較高的値。若使用這種矽靶材進行濺鍍成膜， -16 - 201233822 則顆粒的產生受到抑制，其結果，可得到低缺陷的含矽膜 。已知這種高品質含矽膜除了構成空白光罩基材的光學膜 以外，還能具有各種用途。 [貫施例1]:準備4枚邊長152mm方形之合成石英製 光罩用基板，在各個基板上，藉由DC濺鍍法，使膜厚 76nm 的 MoSiON 膜（Mo : Si : Ο : N= 1 : 4 : 1 : 4 )成膜 。所使用的靶的導電型爲η型且在室溫的比電阻爲60 Ω · c m之單結晶矽之矽靶材與μ 〇 S i燒結靶材（Μ 〇 : S i = 1 : 2 )這兩種。此外，濺鍍氣體採用氬氣、氮氣與氧氣。 使用 Lasertec製的 Magics2351 (註冊商標），對於 以這種方式所得到的MoSiON膜測定缺陷，其結果， 〇. 2 μηι以上的缺陷數平均每枚成膜基板爲8個。 [實施例2]:矽靶材採用導電型爲η型且在室溫的比 電阻爲200 Ω · cm之單結晶矽，將其他的成膜條件設定爲 與實施例1相同，在4枚光罩用基板上進行MoSiON膜的 成膜。在成膜後，與實施例1同樣地測定缺陷，其結果， 0.2 μιη以上的缺陷數平均每枚成膜基板爲6個。 [比較例1 ]:矽靶材採用導電型爲ρ型且在室溫的比 電阻爲0.001 Ω · cm之多結晶矽，將其他的成膜條件設定 爲與實施例1相同，在4枚光罩用基板上進行MoSiON膜 之成膜。在成膜後，與實施例1同樣地測定缺陷，其結果 ，0.2μιη以上的缺陷數平均每枚成膜基板爲21個。 [比較例2]:除了將矽靶材變更爲導電型爲ρ型且在 室溫的比電阻爲1 5 Ω · cm之單結晶矽以外，以與實施例1 -17- 201233822 相同成膜條件嘗試Mo Si ON膜之成膜，其結果， 靶材得到安定的放電。 [產業上之可利用性] 本發明係設計成使用在室溫的比電阻爲2 0 Ω 的矽靶材，使含矽膜濺鍍成膜，因此經過成膜步 特性得以改善，其結果，含矽膜中之顆粒缺陷數 此可提供低缺陷且高品質的含矽膜，亦可利用作 罩基材的遮光膜或相偏移膜等。 無法由矽 _ cm以上 驟，放電 減少。藉 爲空白光 -18-The sputtering method of the present invention is not particularly limited, and DC sputtering is preferred. In addition, the DC sputtering may be a DC sputtering or a pulsed DC sputtering. The ruthenium-containing film associated with the present invention is a ruthenium target having a specific resistance of 20 Ω·cm or more at room temperature, for example, containing a reaction. A reactive sputtering film is formed in an atmosphere of a gas, and the reactive gas system contains at least one of oxygen and nitrogen. The oxygen-containing gas can be exemplified by oxygen gas, nitrogen oxide gas (the oxidation number of nitrogen is not particularly limited), carbon monoxide gas, carbon dioxide gas, or the like. Further, the nitrogen-containing gas may, for example, be nitrogen gas or nitrogen oxide gas (the oxidation number of nitrogen is not particularly limited), ammonia gas or the like. In addition, an inert gas such as argon, helium or ammonia may be used together with these gases. Such a sputtering gas can be appropriately adjusted in order to obtain a desired film composition or discharge stability. The range of the gas pressure may be, for example, 0.01 1 P a -1 0 P a . The blank mask substrate to which the present invention relates is an optical film comprising the above-described ruthenium-containing film of the present invention as a light-shielding film or a phase-shift film. The ruthenium-containing film of the present invention can also be used as a hard mask film for etching a light-shielding film with high precision or as a support film such as an etch stop film provided between a transparent substrate and a light-shielding film. In contrast to conventional tantalum targets, the tantalum target associated with the present invention has a higher electrical conductivity. When such a ruthenium target is used for sputtering film formation, the generation of particles is suppressed from -16 to 201233822, and as a result, a ruthenium-containing film having a low defect can be obtained. It is known that such a high-quality ruthenium-containing film can have various uses in addition to the optical film constituting the blank reticle substrate. [Example 1]: Four substrates of a synthetic quartz reticle having a side length of 152 mm were prepared, and a MoSiON film having a film thickness of 76 nm (Mo : Si : Ο : N) was formed on each substrate by DC sputtering. = 1 : 4 : 1 : 4 ) Film formation. The conductivity type of the target used is n-type and the specific resistance at room temperature is 60 Ω · cm of the single crystal 矽 target and the μ 〇S i sintered target (Μ 〇: S i = 1 : 2 ) Two. In addition, the sputtering gas is argon gas, nitrogen gas and oxygen gas. Using the Magics 2351 (registered trademark) manufactured by Lasertec, the defects of the MoSiON film obtained in this manner were measured. As a result, the number of defects of 2 μηι or more was 8 per film-forming substrate. [Example 2]: The ruthenium target was a single crystal ruthenium having a conductivity type of n-type and a specific resistance at room temperature of 200 Ω · cm, and other film formation conditions were set to be the same as in the first embodiment, and four light beams were used. Film formation of the MoSiON film was performed on the cover substrate. After the film formation, the defects were measured in the same manner as in Example 1. As a result, the number of defects of 0.2 μm or more was six on average per film-forming substrate. [Comparative Example 1]: The ruthenium target was a polycrystalline ruthenium having a conductivity type of p-type and a specific resistance at room temperature of 0.001 Ω·cm, and other film formation conditions were set to be the same as in the first embodiment, and four light beams were used. Film formation of a MoSiON film was performed on the cover substrate. After the film formation, the defects were measured in the same manner as in Example 1. As a result, the number of defects of 0.2 μm or more was 21 per film-forming substrate. [Comparative Example 2] The same film formation conditions as in Example 1 -17-201233822 except that the ruthenium target was changed to a single crystal ruthenium having a conductivity type of p type and a specific resistance at room temperature of 15 Ω · cm. The film formation of the Mo Si ON film was attempted, and as a result, the target was subjected to a stable discharge. [Industrial Applicability] The present invention is designed to use a ruthenium target having a specific resistance of 20 Ω at room temperature to cause a ruthenium-containing film to be sputter-deposited, thereby improving film formation step characteristics, and as a result, The number of particle defects in the ruthenium-containing film can provide a low-defect and high-quality ruthenium-containing film, and can also be used as a light-shielding film or a phase-shift film of a cover substrate. It is impossible to reduce the discharge by 矽 _ cm or more. Borrowing blank light -18-